Process for producing a material containing sodium polyphosphates



Patented Feb. 2, 1954 PROCESS FOR PRODUCING A MATERIAL CONTAINING SODIUM POLYPHOSPH-ATES Bruno Blaser, Dusseldorf-Holthausen,and. Friedrich Weldes, Dusseldorf-Benrath, Gcrmany,.a.ssigners to Hcnkel & Cie G. m. .b.H., Dusseldorf- Holthausen, Germany "NoDrawing. Application October 27 1951,

' 'Serial No. 253,552

8 Claims. (Cl. 252-135) The present invention relates to a process for the production of sodium polyphosphates, having a great immediate solubility in water.

It is known that pyrophosphates, metaphosphates and polyphosphates are produced by dehydrating orthophosphates which have been in-- completely neutralized. The preparation of pyroand metaphosphates differs from that of polyphosphates in that individual chemical compounds are used for preparing the former, while the latter are made from a starting material consisting in a mixture of monoand dialkali phosphates. In order to make sure that a mixture of these salts reacts completely down to the smallest particles one has already used a starting material, containing monosodium phosphate and disodium phosphate in a very fine mixed state and having been prepared by flash-drying finely divided solutions containing both NaHzPO4 and Nazi-IP04. The polyphosphates prepared in this way are said to be very easily soluble in water.

It is the object of this invention to provide a simple and inexpensive process for the production of a solid material containingsodium polyphosphates of higher immediate water solubility than that of products of this kind known heretofore. Other objects and advantages of the process according to the invention will become apparent from the following specification.

It has been pointed out that, in the production of sodium polyphosphates, it is very important to use pure starting materials. If impurities should be present, they should be such as to be volatilized away and not deposited in the residual solid salt mass. Therefore it was very surprising, that sodium polyphosphates, having a content of sodium sulfate from -30% by weight and being prepared from solutions, containing sodium sulfate, have still a greater immediate solubility than sodium polyphosphates, being prepared from pure starting materials.

According to this invention, solutions containing monoand disodium phosphate and sodium sulfate in amounts sufiicient to reach a content of 10-30% by weight in the final product, is flash dried; the dry powder obtained in this way is then heated in any suitable apparatus to volatilize away molecularly bound water and to produce sodium polyphosphate.

Solutions containing monoand disodium phosphates may be obtained in any desired way. They may, for instance, be produced'by reacting pure phosphoric acid. or phosphoric acid containing impurities with caustic alkalies or alkali carbonates; they may, furthermore, be obtained from acid phosphate solutions, such as they re.-

sult from thereaction of superphosphates with sodium sulfate solutions. It is possible too, to add sulfuric .acid or sodium sulfate to any solution of orthophosphates to reach the desired .content of 10-30% by weight sodium sulfate in the final product. The ratio of mono and disodium phosphate is so adjusted as to correspond to the desired ratio of alkalioxide and phosphorous pentoxide in the produced polyphosphate. If the phosphate solution is prepa'red'by reacting superphosphate with a sodium sulfatesolution, a surplus of the latter may be used to introduce the desired quantity of sodium sulfate.

These solutions are processed thereafterbythe usual operations known in the art. The dry mixtures are obtained from the lyes by flash-dry ing, for instance, by spray-drying or by drying on a roller. More particularly, in the spraydrying the hot gases escaping from the polyphosphate furnace can be used for drying the phosphate solution. In thethus obtained dry products, mono-and diphosphates are intimately mixed down to molecular dimensions. .For'dehydrating, the thus obtained products are heated to the required temperatures, if necessary, with addition of substances which accelerate the reaction. The reaction can be brought about either by calcining or by fusing. .In order to shorten the time of reaction, temperatures over 270 C. are applied. It is obvious that the kind of processing thedehydrating step and of cooling the hot sodium polyphosphates has a certain in fluenceon thesolubility of the final product, but in each case, sodium polyphosphates with a content of 10-30% by weight sodium sulfateand being prepared by the process of this invention have a better solubility than sodium polyphosphates containing no or little amounts of so- I diumsulfate only.

It was found that the sulfate contents of the dry starting products impairs neither the dehydration process nor their calcium sequestering properties. As sodium polyphosphates are mostly used as cleaning agents for industrial and household use, their content of sodium sul- S fate is no disadvantage, because such compositions often contain sodium sulfate as builders.

In the-following, the process according to the V invention will be. describedmore fully and illu=strated by examples.

of iilustration'only and'thatmanymodifications of the amount of the components and'other'par I However, it should beunfderstood that these examples are given by'fway ticulars may be made without departing from the spirit of the invention. dissolved productaiter seconds of shaking zxample 2 30 16.6 cu. meters of an aqueous solution con- 5 taming 50 grams Of Nazsoi and 296 grams Of sodium polyphosphate, Percent Percent Percent Percent NaH2PO4 per liter are neutralized with 1.4 tons gifi foiaratas' gm soda to a point where the solution contains WjthoutNBzSO; 50 c4 75 89 NaHzPO4 and NazHPOr in a molar ratio of 1 :1.0. gg g g gfi This mixed phosphate solution is-concentrated 10 milled 59 70 so by heating to a PzOs-content of 298 g./l. and after addition of 50 kg. of NaN O3, which serve Example 3 for the oxidaticirof dark impurities in the sub- To 15 cu. meters of a technical phosphate lye, sequent dehydrating step, sprayed at a temperahi a 15 w ch contains 175 g. P205 per liter m the form ture of 110 C. 6.4 t. of dry powder are obtained of the following composition: 57.5% Nazi-IP04 of 467 per hter and Feand ca-ions as impurities, Z85 kgs. of cal- 27.1% NaI-I2PO4, 12.1% NazSOr, 0.5% water 1nsoluble substances 2 8% moisture and impurities. cmed Soda are t The solutlqn filtered to remove the precipitated impurities and now The material coming from the spraying tower contains 40% of the P205 neutralized to Nazi-IP04. was passed through a gas heated revolving fur nae at a tem erature from C The By evaporatmn on a spraying roller a dry salt is F p obtained in powder form which is subsequently caloination product (5.8 t.) is a white, granular heated. o

in a calciner to 450 C. powder which is readily soluble and has the fol- D 4.65 t. of a product are obtained containing lowing composition. 80.7% NasPaOio, 5.2% (NaPOs): 127% NazSOe 0.2% water-insoluble 26 15% M 5 53% 0f P205 and 32% Na2o- 12% o e assets. a. 521m q g gigi gfi gg a hlgh @P for sequest' sequestering property, it may be assumed that g 1 a mixture of 1 mol NasPsOio and 2 mol of poly- Erample 2 3O mer NaPOa is present. 2.1 t. of Nan-IP04 are added to 10 cu. meters Example 4 of monopmsphate contammg 175 10 cu. meters of Na-diphosphate lye, which NaHzPO-i and 65 g./ l. sodium sulfate, and wh contains 2.4 t. NazHPOr and 0.85 NazSO4 are was partly neutralized with 0.35 t. of NazCOa mixed with 3 (of 783%) and Sprayed and filtered. The mixture is further treated as 35 While rm, The spray-dried powder yields, in Example 1, concentrated, Sprayed and after calcinin in a revolving furnace at 350-400 ca1cined- About 3- Of the calcined Product 0. about 3.4 t. of a product with 24% Nazsoi, are obtained containing 88% NasPsolo and 12% 445% P205 and 295% Nazo' This composition NaZ SO4 aI1d havmg the same Propertles as 40 corresponds to a content of 98% hexasodium scribed 1n Example H tetrapolyphosphate (NasPoOu). The product o w he be lmmedlate s ub hty 0f the has a very good immediate solubility in water. product obtained by the process described in Example 2, its solubility was compared with that Example 5 of a product, being made from starting material To 10 cu. meters of sodium diphosphate lye containing no sodium sulfate. The conditions with 2.4 t. of NazHPO-i, we add 454 kg. sulfuric of processing were the same as described in Exacid B.=78% H2804) and this solution is ample 2. The sulfate free product contained concentrated to about 60% of solid contents and particles, the size of that being a little greater subsequently sprayed while heated. By calcinthan the particle size of the sulfate containing ing the spray-dried powder in a sintering f product. To show that the difference in the 50 nace or other suitable calcining furnace we obimmediate solubilities was not due to the differtain at a temperature of about 350-450 C., ence in the particle sizes, the sulfate-free prodan almost water-free product containing 80% not was milled in a laboratory mill. The dis- NasPaOm, 3% polymer NaPO3, 15% NazSOe. The tribution of particle sizes was as follows: sequestering capacity for calcium is excellent,

particle size in mm.

sodium polyphosphate, 12% Percent Percent Percent Percent Percent incisor 20 22 40 1 5 sodium polyphosphate without NBZSO; 4o 26. s 23 s s, 5 sodium polyphosphate without NazSOr, milled a. 5 2s. 5 as 14 20 To determine the immediate solubility of these which makes it possible to use the product in polyphosphates, samples of 10 g. were shaken cleansing and rinsing compounds, for 2, 5, 10 and 30 seconds with 90 cm. of distilled water. The solids were then filtered off, Example 6 dried and weighted. The dissolved polyphos- 0 kg. Na2HPO4 are dissolved in 15 meters phate given in per cent of the used polyphosof hot water and-after adding 200 kg. sulfuric phat; was as follqws; acid of 78% H2SO4sprayed at a temperature of 105 C. By sintering the spray-dried powder in a calciner at 400-450 0, there is obtained 950 kg. of a mixture, containing about 75% N86P4013 and 23% Na2SO4. The product has a high calcium sequestering capacity and can be used in washing agents.

Example 7 2 cu. meters of a hot solution containing 920 kg. Nazi-IP04 and 163 kg. Neil-121 04 were hot sprayed after addition of 400 kg. NazSO i. The sprayed powder was sintered in a calcinator at a temperature of 350-400 C. There were obtained 1.4 t. of a dry powder containing 38% Na4P207, 32% Na5P301o and 28% NazSOi. The product has a good sequestering capacity for calcium ions, a high immediate solubility in water and is therefore suitable for the use in all kinds of washing, rinsing and cleaning compositions.

Example 8 10 cu. meters of a phosphate lye containing 1000 kg. N31H2PQ4, 1200 kg. Na2HPO4 and 600 kg. NazSOr and being prepared by addition of sulphuric acid to a solution of disodium phosphate were sprayed into a revolving furnace. The furnace was heated by a direct flame. In the furnace the solution was dried and the solid particles molten down at 800 C. under completely dehydrating. After chilling the molten product there Was obtained a material that could easily be milled into a fine powder being very good soluble in water. The mixture contained 21.1% Na2SO4, 26.1% P205 and 31.3% NazO. The molar ratio Na2O:PzO5 corresponds to the formular N2.6P4013. The product has a very good calcium sequestering property.

We claim:

1. A process for producing a material containing sodium polyphosphates which comprises making a solution containing a, mixture of monosodium phosphate, disodium phosphat and sodium sulfate in an amount suiiicient to give a content of 10-30% by weight of sodium sulfate in the final product, flash-drying the solution so as to obtain a mixture of said phosphates and the sulfate in powder form, and heating said powder to a temperature over 270 C., at which conversion of the phosphates into polyphosphates will occur.

2. A process for producing a material containing sodium polyphosphates which comprises making a solution containing a mixture of monosodium phosphate, disodium phosphate and sodium sulfate in an amount sufiicient to give a content of 10-30% by weight of sodium sulfate in the final product, concentrating said solution, flashdrying the concentrate so as to obtain a mixture of said phosphates and the sulfate in powder form, and heating said powder to a temperature over 270 C. at which conversion of the sodium phosphates into sodium polyphosphates will occur.

3. A process for producing a material containing sodium polyphosphates which comprises making a solution containing a mixture of monosodium phosphate, disodium phosphate and sodium sulfate in an amount sufficient to give a content of 10-30% by weight of sodium sulfate in the final product, concentrating said solution, flash-drying the concentrate at a temperature above C. until a dry powder is obtained, and heating said powder at a temperature ranging from 270 C. to 850 C., whereby conversion of the phosphates into polyphosphates occurs.

4. A process according to claim 3 in which conversion of the mixture of phosphates into polyphosphates is brought about by calcining in the temperature range from 270-500 C.

5. A process according to claim 3, wherein conversion of the mixture of phosphates into polyphosphates is brought about by heating to fusion in the temperature range from 650-800 C.

6. A process according to claim 1, wherein the flash-drying is effected by spray-drying.

7. A process according to claim 1, wherein the flash-drying is effected by spraying the solution to be dried into the hot furnace for dehydrating the orthophosphates.

8. A process according to claim 1, wherein the flash-drying is eifected by a hot roller.

BRUNO BLASER. FRIEDRICH WELDES.

References Cited in the file of this patent FOREIGN PATENTS Number Country Date 378,345 Great Britain Aug. 11, 1932 

3. A PROCESS FOR PRODUCING A MATERIAL CONTAINING SODIUM POLYPHOSPHATES WHICH COMPRISES MAKING A SOLUTION CONTAINING A MIXTURE OF MONOSODIUM PHOSPHATE, DISODIUM PHOSPHATE AND SODIUM SULFATE IN AN AMOUNT SUFFICIENT TO GIVE A CONTENT OF 10-30% BY WEIGHT OF SODIUM SULFATE IN THE FINAL PRODUCT, CONCENTRATING SAID SOLUTION, FLASH-DRYING THE CONCENTRATE AT A TEMPERATURE ABOVE 100* C. UNTIL A DRY POWDER IS OBTAINED, AND HEATING SAID POWDER AT A TEMPERATURE RANGING FROM 270* C. TO 850* C., WHEREBY CONVERSION OF THE PHOSPHATES INTO POLYPHOSPHATES OCCURS. 